Article(id=1244280828872737644, tenantId=1146029695717560320, journalId=1243978990336127019, issueId=1244280827157263057, articleNumber=null, orderNo=null, doi=10.7520/1001-4888-24-112, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1720368000000, receivedDateStr=2024-07-08, revisedDate=1723046400000, revisedDateStr=2024-08-08, acceptedDate=null, acceptedDateStr=null, onlineDate=1774589267222, onlineDateStr=2026-03-27, pubDate=1753977600000, pubDateStr=2025-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1774589267222, onlineIssueDateStr=2026-03-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1774589267222, creator=13701087609, updateTime=1774589267222, updator=13701087609, issue=Issue{id=1244280827157263057, tenantId=1146029695717560320, journalId=1243978990336127019, year='2025', volume='40', issue='4', pageStart='387', pageEnd='538', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1774589266813, creator=13701087609, updateTime=1774589721933, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1244282736148595306, tenantId=1146029695717560320, journalId=1243978990336127019, issueId=1244280827157263057, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1244282736148595307, tenantId=1146029695717560320, journalId=1243978990336127019, issueId=1244280827157263057, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=444, endPage=454, ext={EN=ArticleExt(id=1244280829145367410, articleId=1244280828872737644, tenantId=1146029695717560320, journalId=1243978990336127019, language=EN, title=Anti-aging behavior of graphene-coated poly(p-phenylene benzobisoxazole) fibers in the humid environment, columnId=null, journalTitle=Journal of Experimental Mechanics, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Poly(p-phenylene benzobisoxazole) (PBO) fibers have garnered significant attention due to their exceptional mechanical properties, high thermal stability, and flame resistance, demonstrating broad application prospects in aerospace, transportation, and new energy sectors. However, the aging behavior of PBO fibers in humid environments severely compromises their long-term service performance, limiting their development and application in high-tech fields. Therefore, enhancing the anti-aging properties of PBO fibers under humid conditions remains a critical challenge. In this study, the protective effect of graphene coatings on PBO fibers in humid environments was investigated using single-fiber micro-tensile testing. The results indicate that PBO fibers undergo hydrolysis in humid environments, leading to a reduction in Young’s modulus and tensile strength. While coating PBO fibers with covalently cross-linked graphene oxide significantly enhances their mechanical properties, it fails to improve their moisture resistance. Further, the reduction of covalently cross-linked graphene oxide through high-temperature pyrolysis yields reduced graphene oxide with a dense layered stacking structure and excellent hydrophobicity, effectively improving the anti-aging performance of PBO fibers. The reduced graphene oxide-coated PBO fibers exhibit a strength retention rate of nearly 98.2% at 50% relative humidity and up to 96.4% at 80% relative humidity.

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聚对苯撑苯并二噁唑(PBO)纤维由于具有优异的力学性能、高热稳定性和阻燃性等受到广泛的关注,在航空航天、交通运输、新能源等领域拥有广阔的应用前景。然而,PBO纤维在潮湿环境下的老化行为严重影响了材料的长期服役性能,限制了其在高新技术领域的发展和应用,因此如何提升PBO纤维在潮湿环境下的抗老化特性是亟待解决的问题。本文采用纤维单丝微拉伸实验方法,研究了石墨烯涂层对PBO纤维在潮湿环境下的防护作用,结果表明,PBO纤维在潮湿环境下会发生水解,造成弹性模量和断裂强度的降低。使用共价交联氧化石墨烯涂覆于PBO纤维表面能够显著增强其力学性能,但仍无法改善其耐湿性。共价交联氧化石墨烯高温热解制备的还原氧化石墨烯具有致密的层状堆叠结构及良好的疏水性,可以有效提升PBO纤维的抗老化性能。还原氧化石墨烯涂覆的PBO纤维在50%相对湿度下的强度保留率达到98.2%,在80%相对湿度下的强度保留率达到96.4%。

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汪国睿(1990-),男,博士,特任教授。主要研究领域:微纳米力学。Email:
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石墨烯涂覆聚对苯撑苯并二噁唑纤维在潮湿环境下的抗老化行为
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武松梅 1 , 肖俊华 2 , 汪国睿 2
实验力学 | 2025,40(4): 444-454
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实验力学 | 2025, 40(4): 444-454
石墨烯涂覆聚对苯撑苯并二噁唑纤维在潮湿环境下的抗老化行为
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武松梅1, 肖俊华2, 汪国睿2
作者信息
  • 1.安徽职业技术大学现代服装学院,安徽合肥 230011
  • 2.中国科学技术大学近代力学系,中科院材料力学行为和设计重点实验室,安徽合肥 230027

通讯作者:

汪国睿(1990-),男,博士,特任教授。主要研究领域:微纳米力学。Email:
Anti-aging behavior of graphene-coated poly(p-phenylene benzobisoxazole) fibers in the humid environment
Songmei WU1, Junhua XIAO2, Guorui WANG2
Affiliations
  • 1.Department of Textile and Garment, Anhui University of Applied Technology, Hefei 230011, Anhui, China
  • 2.CAS Key Laboratory of Mechanical Behavior and Design of Materials, Department of Modern Mechanics, University of Science and Technology of China, Hefei 230027, Anhui, China
出版时间: 2025-08-01 doi: 10.7520/1001-4888-24-112
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聚对苯撑苯并二噁唑(PBO)纤维由于具有优异的力学性能、高热稳定性和阻燃性等受到广泛的关注,在航空航天、交通运输、新能源等领域拥有广阔的应用前景。然而,PBO纤维在潮湿环境下的老化行为严重影响了材料的长期服役性能,限制了其在高新技术领域的发展和应用,因此如何提升PBO纤维在潮湿环境下的抗老化特性是亟待解决的问题。本文采用纤维单丝微拉伸实验方法,研究了石墨烯涂层对PBO纤维在潮湿环境下的防护作用,结果表明,PBO纤维在潮湿环境下会发生水解,造成弹性模量和断裂强度的降低。使用共价交联氧化石墨烯涂覆于PBO纤维表面能够显著增强其力学性能,但仍无法改善其耐湿性。共价交联氧化石墨烯高温热解制备的还原氧化石墨烯具有致密的层状堆叠结构及良好的疏水性,可以有效提升PBO纤维的抗老化性能。还原氧化石墨烯涂覆的PBO纤维在50%相对湿度下的强度保留率达到98.2%,在80%相对湿度下的强度保留率达到96.4%。

PBO纤维  /  还原氧化石墨烯  /  力学性能  /  单丝拉伸  /  湿度  /  老化

Poly(p-phenylene benzobisoxazole) (PBO) fibers have garnered significant attention due to their exceptional mechanical properties, high thermal stability, and flame resistance, demonstrating broad application prospects in aerospace, transportation, and new energy sectors. However, the aging behavior of PBO fibers in humid environments severely compromises their long-term service performance, limiting their development and application in high-tech fields. Therefore, enhancing the anti-aging properties of PBO fibers under humid conditions remains a critical challenge. In this study, the protective effect of graphene coatings on PBO fibers in humid environments was investigated using single-fiber micro-tensile testing. The results indicate that PBO fibers undergo hydrolysis in humid environments, leading to a reduction in Young’s modulus and tensile strength. While coating PBO fibers with covalently cross-linked graphene oxide significantly enhances their mechanical properties, it fails to improve their moisture resistance. Further, the reduction of covalently cross-linked graphene oxide through high-temperature pyrolysis yields reduced graphene oxide with a dense layered stacking structure and excellent hydrophobicity, effectively improving the anti-aging performance of PBO fibers. The reduced graphene oxide-coated PBO fibers exhibit a strength retention rate of nearly 98.2% at 50% relative humidity and up to 96.4% at 80% relative humidity.

PBO fiber  /  reduced graphene oxide  /  mechanical properties  /  single fiber stretching  /  humidity  /  aging
武松梅, 肖俊华, 汪国睿. 石墨烯涂覆聚对苯撑苯并二噁唑纤维在潮湿环境下的抗老化行为. 实验力学, 2025 , 40 (4) : 444 -454 . DOI: 10.7520/1001-4888-24-112
Songmei WU, Junhua XIAO, Guorui WANG. Anti-aging behavior of graphene-coated poly(p-phenylene benzobisoxazole) fibers in the humid environment[J]. Journal of Experimental Mechanics, 2025 , 40 (4) : 444 -454 . DOI: 10.7520/1001-4888-24-112
聚对苯撑苯并二噁唑(PBO)纤维是强韧的聚合物纤维,其分子结构中的芳香环与噁唑环组成共平面的共轭结构,使单体聚合成具有刚性棒状的高分子链,而直链排列和取向有序性使分子链紧密堆砌,赋予PBO纤维优异的力学性能、高热稳定性和阻燃性。PBO纤维具有极高的强度重量比,在航空航天、交通运输和新能源等领域具有广泛的应用价值。然而,由于PBO纤维在潮湿环境下的力学性能会下降,使其实际应用受到限制,因此,研究如何提高PBO纤维的强度,并抑制其降解一直是材料科学领域关注的问题。目前,改善PBO纤维力学性能的方法主要包括原位聚合[14]和表面涂层[59]。通过原位聚合可在PBO纤维中掺入纳米颗粒[4]、碳纳米管(CNT)[12]、石墨烯[3]等增强体,进而优化PBO分子链的排列和取向,提高纤维链间的相互作用,改善PBO纤维力学性能;或通过表面涂层克服纤维的化学惰性,提高界面相互作用。原位聚合和表面涂层方法可提升PBO纤维的力学性能,但目前对改性PBO纤维在高湿度条件下的老化行为及其降解机制尚缺乏深入的研究。
为了克服PBO纤维的老化降解问题,已有大量文献对PBO纤维展开了多种化学改性研究。LI等[1]研究了二羧酸功能化CNT对PBO纤维的力学增强作用,通过将功能化CNT与PBO单体原位聚合,形成共价键网络以保障高效的应力传递,从而提高了纤维的强度与耐热性。ZHU等[6]开发了化学惰性表面涂覆方法,采用与PBO相容的聚醚酰亚胺包裹二氧化钛纳米颗粒,制成悬浮液并涂覆于PBO纤维表面,待溶剂挥发后,能够获得1层厚度在100 nm以下的保护涂层,该涂层可显著提升纤维的抗紫外老化能力。此外,采用共沉积策略将聚多巴胺和3-氨基丙基三甲氧基硅烷的水解产物稳定锚定在PBO纤维表面,所获得的仿贻贝涂层可使界面剪切强度增加50%,从而使原子氧的耐侵蚀能力及在湿热环境下的抗老化能力显著提升[7]。近年来,随着二维纳米材料研究的兴起,石墨烯等二维材料涂层技术也引起了人们的高度关注[1012],例如,CHEN等[13]用硅烷偶联剂合成了表面接枝氧化石墨烯(GO)涂层的PBO纤维,该表面涂层具有很强的抗原子氧侵蚀能力,同时GO还增强了纤维的界面剪切强度,使PBO纤维增强树脂复合材料性能显著提升。AMROLLAHI等[14]通过原位聚合聚苯胺和GO获得复合涂层,聚苯胺改性的GO涂层相比于GO涂层具有更好的抗紫外线能力、自由基清理能力和分散性,从而可改善基材的抗风化抗腐蚀能力。ZHU等[15]采用两步法在芳纶纤维表面形成聚多巴胺和GO双层涂层,制备出具有高表面活性、热学性能和力学性能优异的抗紫外芳纶纤维。虽然材料科学领域已有诸多工作初步探索了GO防护涂层的应用前景,然而对石墨烯材料能否在潮湿环境下有效防护高性能纤维仍然不清楚,尤其是石墨烯改性PBO纤维的耐湿性和抗老化行为亟待探索。
本文制备了共价交联氧化石墨烯涂层改性PBO纤维及热还原共价交联氧化石墨烯涂层改性PBO纤维,首先将微拉伸力学平台与湿度环境控制系统相结合,进行了PBO纤维在潮湿环境下的单丝拉伸实验;然后通过分析纤维单丝的拉伸力学性能参数,包括弹性模量和断裂强度,探究涂层对改性PBO纤维力学性能和耐湿性能的影响,揭示了PBO纤维在潮湿环境下的老化机理及涂层对纤维的保护机制。
本文采用1种改良的Hummers方法制备氧化石墨烯(GO)[16]。制备流程如图1所示,首先将石墨粉(Zenyatta)分散溶解在体积比为9∶1的硫酸和磷酸混合物中,在50℃下搅拌2 h;然后将高锰酸钾固体缓慢加入到混合物溶液中,在室温下连续搅拌12 h,将混合物溶液倒入冰浴烧杯中,滴加过氧化氢溶液,待溶液反应后将沉淀物转移出来,用水、30%盐酸、乙醇和乙醚先后洗涤;最后用聚四氟乙烯膜过滤得到GO。通过X射线衍射(XRD)表征(图2),可以发现过滤产物的衍射角(θ)在2θ=9.2°处有1个尖锐的GO特征峰,其衍射角明显小于石墨烯特征峰的衍射角(2θ≈22°),这是由于含氧官能团的引入增大了石墨烯层间间距造成的,衍射峰的偏移证明GO已成功制备[17]。将干燥的GO溶解于去离子水中,加入间苯二酚、硼砂和戊二醛溶液后超声处理3 h,然后使用冻干机将材料冷冻干燥24 h便得到共价交联GO。
本研究使用的PBO纤维是日本东洋纺制造的Zylon-HM纤维,其直径约为12μm。通过喷涂的方式在纤维表面制备1层均匀的石墨烯涂层,如图3(a)所示。首先将单根纤维放置在预热至80℃的加热台表面,以增强石墨烯涂层与纤维的界面黏附,使其紧密接触,保持加热台温度恒定,以防止氧化石墨烯在高温下热分解;然后使用高压喷涂枪将1 mg/mL的氧化石墨烯溶液在纤维表面进行多次喷涂,通过规范GO溶液浓度和喷涂次数来保证涂层的均匀性。相比于纯PBO纤维光滑发亮的表面,GO涂层使纤维表面变得粗糙且呈灰黑色。为了验证GO涂层的存在,我们对样品进行拉曼光谱表征和热重分析,表征结果如图3(b)(c)所示。由图3(b)可见,PBO纤维具有多个拉曼特征峰,其中1608 cm-1处较强的特征峰对应于苯基与杂环苯基的伸缩振动,1532 cm-1处的特征峰对应于苯基伸缩与杂环苯基的弯曲振动,1295 cm-1处的特征峰对应于苯基的弯曲振动,1160 cm-1处的特征峰对应于苯基、杂环苯基和噁唑基团的弯曲振动,而921 cm-1处的特征峰对应于醚键的伸缩振动[18]。尽管GO的拉曼特征D-峰(约1353 cm-1)和G-峰(约1605 cm-1)与PBO纤维的拉曼特征峰重合,但是在2729 cm-1和2904 cm-1处的2D-峰和D+D′-峰仍归属于GO,GO特征峰的出现证明涂层已成功制备[1920]。此外,为了检验GO涂层改性纤维的热稳定性,我们进行了热重分析,TG曲线如图3(c)所示,温度在300℃以内时,原始的PBO纤维在整个温度范围内的重量损失只与纤维空隙中残留的水分有关。随着温度由室温升高到100℃以上,那些附着在表面的水分子及形成团簇稳定吸附在纤维缝隙内的水分子逐渐蒸发,温度达到300℃时,PBO纤维的质量分数比初始值只下降了0.8%。对GO涂层改性纤维,90℃下纤维重量开始明显下降,对应于GO涂层吸收的水分蒸发,而当温度升高到200℃时,GO中的含氧官能团开始受热分解,纤维质量急速下降,改性PBO纤维的质量分数下降了2%[21]
为了获取共价交联还原氧化石墨烯(rGO)涂层,将纤维样品放入充满氮气的管式炉中,以5℃/min的升温速率加热至250℃,达到目标温度后恒温保持4 h,再自然冷却至室温。由于PBO纤维具有较好的耐热性,因此在热还原过程中能够维持结构的稳定。XRD结果如图4(a)所示,rGO的(002)峰对应的衍射角从9.2°移动到24.0°,说明rGO层间距相比于GO层间距明显减小,并与纯石墨烯晶体层间距接近,表明rGO片层间的含氧官能团已被去除。与高结晶度石墨烯的尖锐特征峰相比,rGO的特征峰明显变宽,表明其晶体相的晶粒尺寸更小,且结构无序程度更高[22]。rGO在衍射角为43.3°的(001)取向峰对应着碳材料的乱序堆叠结构。通过图4(b)的拉曼光谱可以看出,拉曼峰强度ID/IGIDIG为D-峰和G-峰的强度)比值的增加对应着缺陷密度降低,石墨化程度提高,该结果与文献的结果一致[2326]。鉴于氧化石墨烯的拉曼D-峰和G-峰半峰宽与石墨烯相比显著增大,意味着六方晶格结构中的碳原子由sp3杂化转变为空位缺陷主导,此时热还原过程中ID/IG比值的升高对应着缺陷密度降低[2728]。由图4的结果可知,由于rGO的含氧官能团减少,内部结构相对致密且无序的特点使其可以有效地防止水分子的侵入,从而保持涂层材料的稳定性。
为了测量PBO纤维的力学性能,将其制备为单纤维细丝样品,制备过程如下:首先在硬纸片上加工出方孔,制作回字形的样品架;再从纤维束中抽取出单根纤维丝,将其沿纸框的中心轴线用环氧树脂胶进行点胶固定,保证纤维不能处于弯曲状态,并控制拉伸长度为1 cm。利用光学显微镜观察纤维表面形貌并测量纤维直径,取10个点的直径求平均值作为计算纤维横截面积的平均直径。单轴拉伸实验基于原位微拉伸台(Deben,MTEST 200N)展开,示意图如图5所示。试样夹持时需保证纤维与夹头的加载轴线对齐,并通过调整夹持力防止试样在夹持端滑移。试样装置固定好后,用剪刀将纸框两侧剪断。为了准确确定样品的初始状态,需对样品进行预拉伸,当载荷出现临界转变时,对应点为拉伸起始点,此时置零位移传感器和力传感器数值,开始实验。拉伸实验中采用准静态拉伸的方式测量纤维细丝的应力-应变曲线,其中应力通过力传感器读取的数值除以纤维的平均横截面积计算,应变则通过位移传感器测得的位移变化量除以纤维夹持端的初始长度计算。拉伸速率设为1μm/s,以保证纤维均匀受力,进而获得准确的断裂强度、断裂伸长率及弹性模量等参数。弹性模量通过拟合应力-应变曲线的初始线性段(10%~30%最大应变处)的斜率获得,断裂强度和断裂伸长率则对应最大应力值和相应的最大应变。每1组测试至少需要10根纤维的有效数据作平均处理。
对潮湿环境下纤维的老化实验,我们搭建了1套包括1个长方体有机玻璃腔、1个起泡器和控制气流流速的节流阀的密封环境箱系统,系统工作原理如图6(a)所示。将氮气通入水泡器中获得湿润气体,再将湿润气体与另一路干氮气混合,汇入到装有微拉伸台的环境箱中。通过调控2路气体的比例控制环境湿度,湿度可以在3%~90%精准控制,环境湿度可利用嵌入式湿度传感器进行连续监测。嵌入式湿度传感器的数值由高灵敏度原子力显微镜湿度检测器(Honeywell HIH 4000)校准,湿度的校准曲线如图6(b)所示。潮湿环境老化实验通常在环境箱湿度到达指定数值并稳定4 h后进行,以确保水与纤维充分地相互作用。
PBO高分子是一种苯并唑聚合物,单体中共轭的苯并异恶唑杂环和芳香环可扩大电子云离域的范围,PBO高分子具有的线性刚性分子链结构使其具有优异的力学性能和较高的热稳定性[29]。通过使用微尺度原位拉伸台对纯PBO纤维及石墨烯涂层改性纤维进行准静态拉伸实验,获得的应力-应变曲线如图7(a)所示。通过对图7(a)应力-应变曲线初始线性段进行拟合可以得到纤维的弹性模量,而当纤维发生断裂破坏时,对应着应力的突然降低,因此最大应力值即为纤维的断裂强度。我们统计了3种纤维的弹性模量和断裂强度,结果如图7(b)(c)中的柱状图所示,其中纯PBO纤维的弹性模量可达(51.4±7.7)GPa,断裂强度可达(1.3±0.4)GPa。GO涂层改性PBO纤维的弹性模量提高到(73.7±7.9)GPa,断裂强度达到了(2.5±0.2)GPa,断裂强度几乎是原始纤维的2倍。GO涂层显著提升了纤维的力学性能,这是因为GO中的含氧官能团和共轭π键与PBO的恶唑杂环和芳香环有较强的相互作用,可以传递横向应力,使GO参与承载,从而减少应力集中所致。GO的纳米结构可以填补PBO纤维表面的微小缺陷与孔隙,这种物理黏附机制改善了纤维的力学性能。当我们在GO涂层中引入共价交联时,纤维的弹性模量可提高到(80.3±4.5)GPa,断裂强度可提高到(2.6±0.3)GPa。GO涂层对PBO纤维的力学性能提升效果略低于共价交联GO涂层,原因是GO的强度可达24.7 GPa[30],但其片层堆叠结构在受力时仍会存在相对滑移,从而弱化了力学增强效应[3132]。在GO中引入共价交联结构,能够取代石墨烯层间原本较弱的氢键网络作用,形成更强的共价键连接网络,从而有效抑制石墨烯片层之间的滑移,可进一步提升PBO纤维的稳定性与力学性能。如图7(a)所示,测得的应力-应变曲线存在一定的分散性,其原因如下:其一,样品制备过程中会引入一定程度扭结和缺陷。其二,石墨烯的氧化程度、涂覆厚度和分布均匀性等因素都会影响测量的力学性能。其三,空气湿度对纤维结构和性能影响具有随机性。尽管实验测量有一定的误差,但是对揭示GO的力学增强效应和湿度环境下的老化规律并无影响。
进行单纤维拉伸实验时,在GO涂层改性纤维的应力-应变曲线中偶尔可以观察到拐点(Kink)现象(图8(a))。这一现象可以从以下2方面进行解释:1)纤维在轴向拉伸过程中可能会发生去捻和矫直,导致应力随位移增长出现平台或突降(图8(b))。2)当二维片层的几何尺寸过大时,会与一维纤维的曲率表面之间产生失配,使外层石墨烯无法紧密贴合在纤维表面。在GO的多次喷涂过程中,由于GO局部分布的不均匀性(图8(c)),容易引发团聚现象。这种团聚会使纤维在拉伸时扭转部位的外层更易剥离,进而产生应力突降的跳跃点。
为了探究湿度对PBO纤维性能的影响,我们在湿度环境控制箱内开展纤维单丝拉伸测试,并获取了PBO纤维在不同湿度下的应力-应变曲线,如图9(a)所示。根据图9(a)数据可知,随着湿度的增加,应力-应变曲线的线性段斜率呈现明显的下降趋势,对应着弹性模量的降低。随着湿度的增加,纤维的抗拉强度逐步下降。在相对湿度50%(50%RH)的条件下,抗拉强度从1.34 GPa降低至1.19 GPa,降幅约为11.2%;而在相对湿度为80%的条件下,抗拉强度从1.34 GPa降低至1.16 GPa,降幅约为13.4%。这一现象与湿度对PBO纤维的作用机制密切相关,其主要机制为水解作用(图9(e)):首先,水分子会攻击碳氮双键,导致PBO分子主链上的五元环打开,其中氮原子与氢原子结合形成酰胺键,碳原子与羟基结合形成酚羟基,从而破坏了原有的共轭刚性结构,降低了高分子链的取向度;随后,酰胺键进一步水解,导致高分子链断裂和相对分子质量下降,这体现了水解作用对分子链结构的破坏。此外,水分子还能够渗透到纤维表面缺陷和微裂纹中,从而增大PBO分子链的间距,影响链间应力传递,破坏纤维表层的高取向结构。上述因素共同作用,导致PBO纤维在湿度环境下的力学性能显著弱化。
根据图9(b)的应力-应变曲线可知,尽管共价交联GO涂层对PBO纤维的力学性能有很大提升,但共价交联GO涂层不能有效阻止潮湿环境引起的强度下降。在50%RH和80%RH的条件下,共价交联GO涂层PBO纤维的抗拉强度分别为2.36 GPa和2.28 GPa,与干燥环境下的纤维强度2.5 GPa(图7)相比,分别降低了5.6%和8.8%。综合来看,共价交联GO涂层改性PBO纤维的强度保留率与纯PBO纤维相当(图9(b)),这主要是因为GO涂层具有亲水性所致。GO表面的含氧官能团对环境湿度高度敏感,可以大量吸附空气中的水分子,从而降低石墨烯与PBO纤维的界面相互作用。此外,共价交联的GO网络同样含有一定的孔隙,为水分子提供了扩散和渗透的通道,使水分子仍然能够到达PBO纤维表面进而引起水解反应(图9(d))。
考虑到GO涂层不能有效提高纤维的抗潮湿老化性能,我们对GO涂层进行高温热解处理,从而获得rGO涂层。通过对改性PBO纤维进行准静态拉伸,测得弹性模量和断裂强度为79.1 GPa和2.3 GPa,与共价交联GO涂层相比,热还原对PBO纤维的力学性能影响较小。图10(a)给出了不同相对湿度下rGO涂层改性PBO纤维的应力-应变曲线,其中模量和强度呈现出一定的离散性,可能是由于GO还原不均匀导致的。根据图10(b)给出的不同相对湿度下的强度保留率柱状图可知,rGO涂层纤维在50%RH和80%RH时的强度保留率分别高达98.2%和96.4%,说明热还原可提高GO的疏水性,并形成更加致密的层状结构,能够有效抑制水分子的附着和渗透,从而能够显著增强PBO纤维对高湿度环境的抵抗力。
本文基于原位微拉伸力学装置和环境湿度控制系统开展了PBO纤维在潮湿环境下的力学性能研究,制备了rGO涂层,并通过微观结构表征探究了rGO涂层对改性PBO纤维抗老化行为的防护机制,得出以下结论:
1)PBO纤维在潮湿环境下会发生水解,造成弹性模量和断裂强度的降低。
2)通过引入GO涂层改性PBO纤维可显著提高其力学性能,但仍无法在高湿度条件下提供有效防护,这主要是由于GO的亲水特性及多孔隙结构引起水分子渗透涂层导致的。
3)通过高温还原获得的rGO涂层具有致密的层状堆叠结构及良好的疏水性,可以有效提升PBO纤维的抗老化性能。
本文从湿度作用下的老化机制出发,提出了基于石墨烯纳米涂层改性PBO纤维的思路,该方法中所涉及的rGO高温喷涂策略可通过大规模、工程化制备对纤维材料进行改性,获得的改性PBO纤维能够满足航天飞行器等工业领域对轻质高强纤维在潮湿环境下的防护需求。
  • 航空科学基金项目(2024Z057078001)
  • 国家自然科学基金项目(12202430; 12241202)
  • 中国科学技术大学青年创新重点基金项目(YD2090002011)
  • 安徽省纤维检验局生丝检测设备自动化系统改造项目(GN2023-18-7594)
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2025年第40卷第4期
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doi: 10.7520/1001-4888-24-112
  • 接收时间:2024-07-08
  • 首发时间:2026-03-27
  • 出版时间:2025-08-01
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  • 收稿日期:2024-07-08
  • 修回日期:2024-08-08
基金
航空科学基金项目(2024Z057078001)
国家自然科学基金项目(12202430; 12241202)
中国科学技术大学青年创新重点基金项目(YD2090002011)
安徽省纤维检验局生丝检测设备自动化系统改造项目(GN2023-18-7594)
作者信息
    1.安徽职业技术大学现代服装学院,安徽合肥 230011
    2.中国科学技术大学近代力学系,中科院材料力学行为和设计重点实验室,安徽合肥 230027

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汪国睿(1990-),男,博士,特任教授。主要研究领域:微纳米力学。Email:
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2种不同金属材料的力学参数

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Genus
种数
Number of
species
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Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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